2-Amino-2,6-dinitrophenylhydrazines

ABSTRACT

3-amino-2,6-dinitrophenylhydrazines of the formula   WHEREIN Y is halogen, haloalkyl carbamyl, lower alkyl substituted carbamyl, carboxyl, lower alkoxy carbonyl, trifluoromethyl, nitro or cyano; Z is amino which is optionally substituted with lower alkyl, lower alkoxy, substituted lower alkyl, substituted lower alkoxy or mono or di-lower alkylamino, with the proviso that not more than one of the substituents is alkoxy, substituted alkoxy or mono or di-lower alkylamino; R1 is H, lower alkyl or lower alkenyl, said alkyl and alkenyl groups are optionally substituted with halogen, lower alkoxy, phenyl or cycloalkyl; R2 and R3 are independently H, C1-C5 alkyl, C2-C5 alkenyl, said alkyl and alkenyl groups are optionally substituted with cycloalkyl groups; R2 and R3 can also be taken together with the nitrogen atom to which they are linked forming the ring structures piperidino, hexamethylenimino, morpholino, or 4methylpiperazino. These compounds are very active plant growth regulators and are particularly useful as herbicides and in tobacco sucker control.

United States Patent [191 Wilcox June 24, 31975 1 12-AMlNO-Z,6-DINITRO1PHENY1LHYDRA- ZlNES [76] Inventor: Merrill Wilcox,2911 NW. 30th [52] US. (111. 260/569; 260/239 B; 260/2472 B; 260/2475 R;260/268 N; 260/293.72;

{51] lnt. (ll. C076 l09/04 [58] Field of Search 260/569; 424/330; 71/121[56] References Cited UNITED STATES PATENTS 3,745,215 7/1973 Kangars260/569 X Primary Examiner-R. V. Hines Attorney, Agent, or Firm-HarryFalber; Frederick H. Rabin; Philip l Berestecki [57] ABSTRACT3-amino-2,6-dinitrophenylhydrazines of the formula 1 2 Y N-N wherein Yis halogen, haloalkyl carbamyl, lower allcyl substituted carbamyl,carboxyl, lower alkoxy carbonyl, trifluoromethyl, nitro or cyano; Z isamino which is optionally substituted with lower alkyl, lower alkoxy,substituted lower alkyl, substituted lower alkoxy or mono or di-loweralkylamino, with the proviso that not more than one of the substituentsis alkoxy, substi tuted alkoxy or mono or di-lower alkylamino; R is H,lower alkyl or lower alkenyl, said alkyl and alkenyl groups areoptionally substituted with halogen, lower alkoxy, phenyl or cycloalkyl;R and R are indepen dently ll, C -C alkyl, C -C alkenyl, said alkyl andalkenyl groups are optionally substituted with cycloalkyl groups; R andR, can also be taken together with the nitrogen atom to which they arelinked forming the ring structures piperidino, hexamethylenimino,morpholino, or 4-methylpiperazino.

These compounds are very active plant growth regulators and areparticularly useful as herbicides and in tobacco sucker control.

110 Claims, No Drawings 3,891,706 llZ-AIvIINo-mpIIsIIIrrtoIPIIIENYIII-IYpItAZINIEs N02 DESCRIPTION or THEINVENTION R $2 The present invention concerns3-amino-2,6-dinitrophenylhydrazines, methods for regulating plant growthwith said compounds, and compositions containing said compounds asactive substances. The compounds of the present invention areparticularly useful as herbicides and agents for the control of tobaccosuckers.

More particularly, the invention concerns 3-amino-2,6-dinitrophenylhydrazines of the formula N02 R R I (I) Y NN R 2 NO 3wherein Y is halogen (preferably Cl or Br), haloalkyl trifluoromethyl,carbamyl, lower alkyl substituted carbamyl. carboxyl, loweralkoxycarbonyl, nitro or cyano; Z is amino which is optionallysubstituted with lower alkyl, lower alkoxy, substituted lower alkyl,substituted lower alkoxy or mono or di-lower alkylamino with the provisothat not more than one of the substituents is alkoxy, substituted alkoxyor mono or dilower allcylamino; R is hydrogen, lower all yl or loweralkenyl, said alkyl and alkenyl groups are optionally substituted withhalogen (preferably Cl or Br), lower alkoxy, phenyl or cycloalkyl(preferably C -C cycloalkyl); R, is preferably H; R and R areindependently H, C -C alkyl (preferably C -C alkyl), C -C alltoxy(preferably C,-C alkoxy), lower alkoxyalkyl, or C -C alkenyl (preferablyC -C alkenyl), said alkyl, alkoxy, alkenyl, and alkoxyalkyl groups areoptionally substituted with cycloalltyl groups (preferably C Ccycloalkyls); R and R can also be taken together with the nitrogen atomto which they are linked forming the ring structures piperidino,hexamethyleneimino, morpholino, or 4-rnethylpiperazino. I

Especially useful are those compounds within the scope of formula (l)which have the formula wherein Y is chloro, trifluorornethyl, nitro orcyano; Z is amino or amino substituted with C -Cl; alkyl or all citywith the proviso that not more than one of the substituents is alkoxy; Ris C,-C alkyl or H; R and R are independently i-i, C -C alkyl; R and Rare taken together with the nitrogen atom to form piperidino.

Particularly preferred compounds have the formula wherein Y is chloro,trifluorornethyl, nitro or cyano; Z is amino; R is H; R and R areindependently C -C alkyl.

The following compounds are particularly useful in this invention:2-(3-amino-2,6-dinitro-4- trifluoromethylphenyl)-l,l-dimethylhydrazine,2-(3- amino-2,6-dinitro-4trifluoromethylphenyl l l'diethylhydrazine,2-(3-amino-4-chloro-2,6- dinitrophenyl)-l,l-diethylhydrazine, and2-(3-amino- 4-chloro-2,o-dinitrophenyl-l ,1-dimethylhydrazine.

The following compounds are particularly useful in tobacco suckercontrol: 2-(3 amino-2,6-dinitro-4- trifluoromethylphenyl)- I.l'dethylhydrazine, 2-( 3- arnino-2,6-dinitro-4-trifluoromethylphenyl)-l l -dimethylhydrazine, 2-(3-amino-2,6-dinitro-4-chlorophenyl)l,l-diethylhydrazine, and 2-(3-amino-2,6-dinitro-4-chlorophenyl )-l .l-dimethylhydrazine.

The herbicidal compounds of the present invention can of course beformulated and applied in accordance with a wide variety of conventionalagronomic techniqucs. Conveniently herbicidal formulations are preparedcontaining about 2 by weight active ingredients and are applied at arate of about 0.5 30 lbs. per acre. When the compounds of the presentinvention are used for tobacco sucker control they are preferablyapplied at a rate of about 10 to about 400 milligrams per plant.

Compounds of formula (i) can be prepared by reacting substantiallyequimolar amounts of a 2-nitro-l,3-

with a hydrazine of formula (ill) R1 is (III) in the presence of an acidacceptor such as an alkylamine of formula (1W) (lV) Add in thesestructures, Y, Z, R R and R have the meanings ascribed to them informula (l), and A represents lower alkyl. These reactants are dissolvedin a suitable aprotic solvent, such as tetrahydrofuran, a dioxane, orlow molecular weight ethers. A precipitate of trialkylaminehydrochloride appears and is filtered off. The supernatant is thensubjected to a similar reaction with 5 ZH and AN (both of which may besimply NH to yield the 3amino-2,6-dinitrophenylhydrazine of formula (I).If ZH equals R R NR,NH, the two steps may be simultaneous.

The starting materials are readily available or can be prepared bymethods well-known in the art. Thus, compounds of formula (Il) may beprepared by nitration of an appropriate chlorobenzene or replacement ofthe -OH group of a nitrophenol by a chlorine atom. Details concerningthe preparation of representative examples of those compounds may befound in Bunnet, et al., J.A.C.S. 76, 3936-39 (1954), Friedrich, et al.,US. Pat. No. 2,257,093 (Sept. 30, 1944), Soper U.S. Pat. No. 3,442,639(May 6, I969), U.S. Pat. No. 3,586,725 to Hunter.

The hydrazines of formula (lll) are either commercially available or maybe prepared by amination of dialkylamines with chloramine orhydroxylamine-O- sulfonic acid or catalyzed ammonia or by reduction ofdialkylnitrosamines.

The trialkylamine of formula (IV) functions as an acid acceptor. In lieuthereof, other compounds which will form an insoluble salt in thereaction may be used. These compounds include pyridines andalkylpyridines, alkali metal hydroxides, excess substituted hydrazine,or other acid acceptors well-known in the art. It is advantageous to useexcess hydrazine as the acid acceptor, since the resulting hydrazinehydrochloride may be treated with an inorganic base, thus recoveringthe'substituted hydrazine. i

The 3-amino-2,6-dinitrophenylhydrazines of formula I, mixed togetherwith the usual additives, are used as herbicidal agents. Furthermore,the active substances can be mixed with fertilizers and applied in thisform. The range of activity of the compounds of the invention can bewidened by applying them in admixture with other herbicides, e.g., withtriazines such as halogendiamino-s-triazines, alkoxyandalkylthiodiamino-striazines, diazines such as uracils, pyridazines,phenols, aliphatic carboxylic acids and halogen carboxylic acids,halogenated benzoic acids and halogenated phenylacetic acids,aryloxyalkane carboxylic acids and aryloxyalkane sulfonic acids,pyridine caroxylic acids, amides, thioamides, hydrazides, esters andnitriles of similar carboxylic acids, carbamic acid esters andthiocarbamic acid esters, quaternary ammonium compounds, ureas,inorganic salts, etc., especially with:

2-chloro-4,6-bis-( ethylamino)-s-triazine2chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis-(methoxypropylamino )-s-triazine 2-methoxy-4,6-bis-( isopropylamino)-s-triazine 2methylthio-4-methoxypropylamino-isopropylamino-s-triazine2-methylthio4,6-bis-( isopropylamino )-s-triazine2-methylthio-4,6-bis-(ethylamino )-s-triazine2-methylthio-4-ethylamino-6-isopropylamine-striazine 2-methoxy-4,6-bis-(ethylamino)-s-triazine 2methoxy-4-ethylamino-6isopropylamino-s-triazine2-chloro-4,6-bis-(isopropylamino)-s-triazine5-bromo-3-sec.butyl-6-methyl-uracil 3-cyclohexyl-5,-trimethylene-uracilcarboxylic 2-methoxy-3,5,6-trichlorobenzoic acid and salts thereof2-methoxy-3,6-dichlorobenzoic acid and salts thereof3-amino-2,5dichlorobenzoic acid and salts thereof3-nitro-2,5dichlorobenzoic acid and salts thereof2-methyl-3,5-dichlorobenzoic acid and salts thereof2-methyl-3,S-dichlorobenzoic acid and salts thereof2,6-dichlorobenzonitrile 2,6-dichloro-thiobenzamide2,3,6-trichlorophenyl acetic acid and salts thereof2,4-dichlorophenoxyacetic acid and salts thereof2,4,5-trichlorophenoxyacetic acid and salts and esters thereof(2-methyl-4-chlorophenoxy)-acetic acid and salts and esters thereof2-(2,4,5trichlorophenbxy)-propionic salts and esters thereof 2-( 2 ,4 ,5trichlorophenoxy )-ethyl-2 ,2- dichloropripionate4-2',4-dichlorophenoxy)-butyric acid and salts and esters thereof4-(2methyl-4'-chlorophenoxy )-butyric acid and salts and esters thereof2,3,6trichlorobenzyloxypropanol 4-amino-3,5,6-trichloropicolinic acidN-cyclooctyl-N,N-dimethyl urea dimethyl urea 3-(4'-chlorophenyl)-1,l-dimethyl urea 3-(3 trifluoromethylphenyl)-l ,l-dimethyl urea 3-( 3',4'-dichlorophenyl)-l l dimethyl urea 3-( 3 ',4'-dichlorophenyl)- ln-butyl- 1 methyl urea 3-(3',4'-dichlorophenyl)-1,1 ,3-trimethyl urea3-(3'4-dichlorophenyl)-1,l-diethyl urea 3-(4'-chlorophenyl)- 1 methoxy-1 methyl urea 3-(3 ,4'-dichlorophenyl)- l methoxy- 1 methyl urea3-(4'-bromophenyl)-methoxy- 1 methyl urea 3-( 3 ,4 '-dichlorophenyl)-3-methoxyl l -dirnethyl urea 3-(4-chlorophenoxyphenyl )-l l dimethylurea N,N-di-(n-propyl)-S-ethyl-thiolcarbamic acid esterN,N-di-(n-propyl)-S-n-propyl-thiolcarbamic acid esterN-ethyl-N-(n-butyl)-S-n-propyl-thiolcarbamic esterNphenyl-O-isopropyl-carbamic acid ester N-(m-chlorophenyl)-O-isopropyl-carbamic ester N-(m-chlorophenyl)-O-(4'chloro-2'-butinyl)- carbamic acid ester N-( 3 ,4dichlorophenyl)O-methyl-carbamic ester. The subject herbicides haveutility in that they control tobacco suckers very well, are highlysoluble in many organic solvents and are particularly effective asherbicides against a variety of grasses and solanacious acid and3-pheriyl-l l acid acid

acid

weeds such as for example weeds of the genera Digitaria, Echinochloa,Setaria, Solanum, Datura, Physalis. See also, other weeds described byQ. P. Soper, US. Pat. No. 3,257,190.

The production of herbicidal compositions according to the invention iscarried out in a manner well-known in the art by the intimate mixing andgrinding of the active substances of the general formula I with suitablecarriers, optionally with the addition of dispersing agents or solventswhich are inert to the active substances. The active substances canexist and be used in the following forms: as solids: dusts, sprinklingagents, granulates, coated granules, impregnated granules andhomogeneous granules;

as concentrates of active substances dispersible in water: wettablepower, pastes, emulsions;

as liquids: solutions, aerosols.

To produce the solid forms (dusts, sprinkling agents, granulates), theactive substances are mixed with solid carriers. Suitable carriers are,e.g., kaolin, talcum, bole, chalk, limestone, ground limestone,dolomite, diatomaceous earth, precipitated silicic acid, alkaline earthsilicates, sodium and potassium aluminum silicates (feldspar and mica),calcium and magnesium sulfates, magnesium oxide, ground syntheticplastics, fertilizers such as ammonium sulfate, ammonium phosphate,ammonium nitrate, ureas, ground vegetable products such as grain flour,bark flour, sawdust, ground nut shells, cellulose powder, residues ofplant extractions, activated charcoal, etc.. These carriers can be usedseparately or they can be mixed with each other. i

The grain size of the carriers is, for dusts, advantageously up to ca.0.1 mm, for sprinkling agents it is ca. 0075 to 0.2 mm and forgranulates 0.2 mm upwards.

The concentrations of active substances in the solid preparations are,as a rule, 0.5 to 80% of the total weight.

To these mixtures can also be added additives which stabilize the activesubstance and/or non-ionic, anionactive and cation-active substances,which, for example, improve the adhesion of the active substances onplants and parts of plants (glues and adhesives) and/or ensure a betterwettability (wetting agents) and also dispersibility (dispersingagents). The following are examples of adhesives: olein-chalk mixtures,cellulose derivatives (methyl cellulose, carboxymethyl cellulose),hydroxyethyl glycol ethers of monoand di-alkyl phenols having 5 toethylene oxide radicals per molecule and 8 or 9 carbon atoms in thealkyl radical, lignin sulfonic acids, their alkali and alkaline earthmetal salts, polyethylene glycol ethers, fatty alcohol polyethyleneglycol ethers having 5 to ethylene oxide radicals per molecule and 8 to18 carbon atoms in the fatty alcohol part, condensation products ofethylene oxide, propylene oxide, polyvinyl pyrrolidones, polyvinylalcohols, condensation products of urea/formaldehyde as well as Latexproducts.

Concentrates of active substances which can be dispersed in water(wettable powders), pastes and emulsion concentrates, are agents whichcan be diluted with water to give any desired concentration. Theyconsist of active substances, carriers, optionally additives whichstabilize the active substance, surface agent substances and antifoamingagentsand, optionally, solvents. The concentration of active substancein these agents is 5 to 80% of the total weight of the latter.

The wettable powders and pastes are obtained by mixing and grinding theactive substances with dispersing agents and pulverulent carriers insuitable devices until homogeneity is attained. Suitable carriers are,for example, those previously mentioned for solid preparations. It isadvantageous in some cases to use mixtures of different carriers.Suitable dispersing agents are, e.g., condensation products ofsulfonated naphthalene and sulfonated naphthalene derivatives withformaldehyde, condensation products of naphthalene or of naphthalenesulfonic acids wtih phenol and formaldehyde, also alkali, ammonium andalkaline earth metal salts of lignin sulfonic acid, also alkylarylsulfonates, alkali and alkaline earth metal salts of dibutyl naphthalenesulfonic acid, fatty alcohol sulfates such as salts of sulfated fattyalcohol glycol ethers, the sodium salt of oleyl ethionate, the sodiumsalt of oleyl methyl tauride, ditertiary acetylene glycols,dialkyldilauryl ammonium chloride and fatty acid alkali and alkalineearth metal salts.

Examples of anti-foaming agents are: silicones, etc. The activesubstances are so mixed, ground, sieved and strained with theabove-mentioned additives that the solid particle size in wettablepowders does not exceed 0.02 0.04 mm and, in the case of pastes, 0.003mm. To produce emulsion concentrates and pastes, dispersing agents suchas those states in the previous sections, organic solvents and water areused. Examples of solvents are: alchols, benzene, xylenes, toluene,dimethyl sulfoxide and mineral oil fractions boiling between and 350C.The solvents must be practically without smell, not phytotoxic, inert tothe active substances and not easily flammable.

In addition, the agents according to the invention can be used in theform of solutions. For this application, the active substance orsubstances of the general formula l are dissolved in suitable organicsolvents, mixtures of solvents or in water. Aliphatic and aromatichydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes,mineral oils, on their own or mixed with each other, can be used asorganic solvents. The solvents should contain the active substanceswithin a concentration range of l to 20% calculated on the total weightof the resulting solution.

Other biocidal active substances or agents can be mixed with thedescribed compositions according to the invention. Thus, in addition tothe stated compounds of the general formual I and other herbicides, thenew agents can also contain, e.g., insecticides, fungicides,bactericides, fungistatics, bacteriostatics or nematocides in order towiden the range of action. The compositions according to the inventioncan also contain fertilizers, micronutrients, etc.

Forms of preparation of these active substances are described in thefollowing. Where not otherwise expressly stated, the terms parts andpercentage are given by weight.

Wettable Power The following constituents are used to produce a) a 10%wettable powder, and b) a 25% wettable powder: a) 10 parts of2-(3-amino-2,6-dinitro-4-trifluoromethylphenyl l l -diethylhydrazine. l0pans of lignin sulfonic acid calcium salt 2 parts of adhesive consistingof 50% polyvinylpyrrolidone and 50% Champagne chalk Continued 38 partsof kaolin 40 parts of Champagne chalk b) 25 parts of2-(3amino-2,6-dinitro-4-trifluoromethylphenyl )-l I dimethylhydruzineparts of condensation products of naphthalene sulfonic acid, phenolsulfonic acids and formaldehyde in the ratio 3:2:().5 4 pans of dibutylnaphthyl sulfonate sodium salt 1 part of methyl-oleyl-tauride sodiumsalt l5 parts of silicic acid 25 parts of neutral sodium aluminumsilicate 25 parts of kaolin Emulsion Concentrate The followingconstituents are mixed together to produce a 25% emulsion concentrate:

parts of 2-( 3-amino-4-chloro-2,6-dinitrophenyl)-l l-diethylhydrazineparts of methylethylketone parts of xylol and parts of isooctylphenylpolyethylene glycol This concentrate can be diluted with water to obtainemulsions of suitable concentrations. Such emulsions are suitable forcontrolling weeds in cultivated plantations, for which purposeapplication of amounts of 5 about 0.5 to 4.lbs. of a compound of formula(I) per acre of treated soil is recommended.

The following examples are intended to illustrate some of theembodiments of the present invention. The examples therefore are. forillustrative purposes only and are not to be construed as limitations.

EXAMPLE 1 Under a nitrogen atmosphere, 4.5 gms. 2,4-dichloro-3,S-dinitrobenzotrifluoride were dissolved in 70 ml. tetrahydrofuran.The solution was cooled to l4C. A solution of 1.6 gms. triethylamine and1.4 gms. l,l-diethylhydrazine in ml. tetrahydrofuran was added slowly,so that the temperature did not rise above -10C. The bottle containingthe reaction mixture was capped tightly, the while maintaining anitrogen atmosphere. The reactants were then allowed to come to ambienttemperature during 8 hrs. and remain thusly for 3 days. The solution wasthen filtered to remove the triethylamine hydrochloride precipitate andput into a stainless steel reaction vessel, purged with nitrogen gas,and cooled to C. An excess of liquid anhydrous ammonia was then run intothe reaction vessel. The temperature was maintained at 20C for 24 hrs.The vessel was vented and allowed to rise to room temperature. Thecontents were reduced in volume until there was a noticeable increase inviscosity, at which point 60-90 petroleum ether was used to precipitatecrude 2-( 3-amino-2,6-dinitro-4trifluoromethylphenyl l ldiethylhydrazine, m.p. 99-l05C. Recrystallization from ethyl ether andligroine gave m.p. l02l05C.

EXAMPLE 2 sphere were dissolved 4.5 gms. 2,4-dichloro-3,5-dinitrobenzotrifluoride. The solution was cooled to l4C. A solution of3.2 gms. triethylamine and 2.8 gms. l,l-diethylhydrazine in 30 ml.tetrahydrofuran was added at such a rate that the temperature did notrise past l0C. While continuing to maintain the nitrogen atmosphere, thebottle containing the reaction mixture was capped tightly and allowed tocome to room temperature during a period of 4 hrs. After standing for 7days at room temperature, the bottle was opened, the precipitate oftriethylamine hydrochloride filtered off, and the solvent removed toyield 2',4'- bis( 2,2-diethylhydrazino )-3 ,5 '-dinitrobenzotrifluoride,a red oil.

EXAMPLE 3 Into 90 ml. tetrahydrofuran under a nitrogen atmosphere weredissolved gms. 2,4-dichloro-3,5- dinitrobenzotrifluoride. The solutionwas cooled to -20C. A solution of 1.6 gms. of triethylamine and 1.4 gms.l,l-diethylhydrazine in 20 ml. tetrahydrofuran was added slowly, so thatthe temperature did not rise above l0C. While continuing to maintain thenitrogen atmosphere, the bot'tle containing the reactants was cappedtightly and allowed to rise to ambient temperature during a period of 4hrs. After several days, the bottle was opened, the triethylaminehydrochloride precipitate filtered out, and the reaction mixture cooledto l7C under a nitrogen atmosphere. A solution of 1.6 gms. triethylamineand 1.0 gms. of N,O-dimethylhydroxylamine in 15 ml. tetrahydrofuran wasthen added slowly, so that the temperature rose to l5C. While stillmaintaining the nitrogen atmosphere, the bottle containing the reactantswas capped tightly and allowed to stand several days at ambienttemperature. The precipitate of triethylamine hydrochloride was filteredout and .the solvent removed to I yield2-(3-(.N-methoxy-N-methylamino)-2,6-dinitro-4- lnto ml. tetrahydrofuranunder a nitrogen atmo- I trifluoromethylphenyl)-l,l-diethylhydrazine, ared oil.

EXAMPLES 4 22 The following were prepared by the methods of Examples l3. v

g 4. 2-(3amino-Z',6'-dinitro-4'- trifluoromethylphenyl l lpentamethylenehydrazine 5. 2-(3 '-amino-2,6'-dinitro-4'-trifluoromethylphenyl )-l l-diallylhydrazine 6.2-(3-amino-2,6dinitro-4'-trifluoromethyl)-lmethyl- 1 propylhydrazine 7.2-(3-amino-2',6'-dinitro-4'- trifluoromethypheny )-l l,2-trimethylhydrazine 8. 2-( 3 '-methylamino-2 ,6 -dinitro-4trifluoromethylphenyl )-l l diethylhydrazine 9.2-(3-methylamino-2',6-dinitro-4-trifluoromethylphenyl)-1,1-dimethylhydrazine l0.2-(3'-methylamino-2,6'-dinitro-4'- trifluoromethylphenyl l ldiallylhydrazine l l. 2-( 3 '-methylamino-2 ',6'-dinitro-4trifluoromethylphenyl l l ,Z-trimethylhydrazine l2. 2-( 3-dimethylamino-2',6'-dinitro-4- trifluoromethylphenyl)- l ldiethylhydrazine 13. 2-( 3 -dimethylamino-2,6 '-dinitro-4'-trifluoromethylphenyl l l -dimethylhydrazine l4. 2-( 3 -dimethylamino-2,6 '-dinitro-4- trifluoromethylphenyl l l diallylhydrazine l5. 2-( 3'-propylamino-2 ,6-dinitro-4- trifluoromethylphenyl l l-dimethylhydrazine l6. 2-(3-amino-4'-chloro-2,6'-dinitrophenyl)-l,l-

dimethylhydrazine hexamethylenehydrazine EXAMPLE 27 2-(3-amino-4-chloro-2,o-dinitrophenyl l 1 -diethylhydrazine is prepared bythe method of Example 1 by substitutingl,2,4,-trichloro-3,S-dinitrobenzene for the l8.2-(3-amino-4-chloro-2,6-dinitrophenyl)-l.1- EXAMPLES 23 3Odiallylhydmzine I The following were prepared by the method of Exam- 19.2',4--bis(2,2-dimethylhydrazino)-3,5-d1n1trobenl 1 3:

zotrifluoride 28. 2-(3-amino-4-cyano-2',6'-dinitrophenyl)-l,1- 20.2,4'-bis(2,2-dimethylhydrazino)-3,S-dinitrodiethylhydrazine hloro n 29.2-(3'-amino-4'-carbamyl-2,6-dinitrophenyl)- 21. 2,4-'-bis(2,2-diethylhydrazino)-3 ,S-dinitro- 1 1 .diethylhydrazine chlorobenzene30. 2-(3amino-4-'-methoxycarbonyl 2' 6- 22.2-(3-methoxyamino-2,6-dinitro-4-chlorophenyl)- dinitrophenyl)-l,l-diethylhydrazine l,l-dimethylhydrazine l claim:

ii. A compound of the formula EXAMPLE 23 The compound of Example 1,i.e., 2-(3-amino-2,6- Y dinitro dtrifluoromethylphenyl)-l,l-diethylhydrazine, nitralin and trifluralinwere applied pre-emergent to 1 several species at one lb. per acre andstand and growth 25 ratings made 4 days later. These data were obtained.Z 2

Cmpd of Ex. l nitralin trifluralin check stand growth stand growth standgrowth stand growth ryegrass 0 0 l0 l0 100 l()() corn )0 100 60 100 30100 I00 sunflower 100 80 I00 20 lot) 60 100 I00 tomato 90 10 too 50 10030 100 I00 mustard 8t) 30 100 50 lot) 100 I00 EXAMPLE 24 wherein Y ishalogen or trifluoromethyl; Z is amino or W mono or di-lower alkylamino;R is H. lower alkyl or The PQ l and N butyl 4 tert lower alltenyl; and Rand R are independently l-l, butyl-l,o-dmitroanllme were each applled to18 tolower alk 1 O lowsr awe] l bacco plants one day after removal ofthe inflores- 40 r cences, each plant receiving 50 ml. containing 1,500ppm active ingredient in 50% aqueous acetone. Three weeks later thesuckers were counted and the results were:

No. suckers/l8 plants Check 1 l6 N-sec-butyll-tert-butyl-Z.

o-dinitroaniline 13 Compound of Example I 1 EXAMPLE 25 The procedure ofExample 1 is followed exactly re- 2. A compound of claim wherein Y ischloro or trifluoromethyl; Z is amino or amino substituted with C -Calkyl; R is H or C -C alkyl; and R and R are independently H, or C Calkyl.

3. A compound of claim 1 wherein Y is chloro or trifluoromethyl; Z isamino; R is H; and R and R are independently C -KC alkyl.

4. A compound of claim It which is 2-(3-amino-2,6-dinitro-4-trifluoromethylphenyl)-1,ldimethylhydrazine.

5.. A compound of claim 1 which is 2-(3-amino-2,6-dinitro-4-trifluoromethylphenyl)-1,l-diethylhydrazine.

6. A compound of claim l which is 2-(3-amino-4-chloro-2,6-dir1itrophenyl)- l l-diethylhydrazine.

7. A compound of claim 1 which is 2-(3-amino-4-trifluoromethyl-2,o-dinitrophenyl)- l ,l ,2-trimethylhydrazine.

A compound of claim 1 which is 2-(3methylamino-4-trifluoromethyl-2,6-dinitrophenyl)- l,l-diethylhydrazine.

9. A compound of claim E which is 2'(3-dimethylamino-Z,6dinitro-4-trifluoromethylphenyl)-l,l-dimethylhydrazine.

Ml). A compound of claim T which is 2-(3-propylamino-2,6-dinitro-4-trifiuoromethylphenyl )-l ,ldimethylhydrazine.

1. A COMPOUND OF THE FORMULA
 2. A compound of claim 1, wherein Y ischloro or trifluoromethyl; Z is amino or amino substituted with C1-C4alkyl; R1 is H or C1-C4 alkyl; and R2 and R3 are independently H, orC1-C3 alkyl.
 3. A compound of claim 1 wherein Y is chloro ortrifluoromethyl; Z is amino; R1 is H; and R2 and R3 are independentlyC1-C3 alkyl.
 4. A compound of claim 1 which is2-(3-amino-2,6-dinitro-4-trifluoromethylphenyl)-1,1-dimethylhydrazine.5. A compound of claim 1 which is2-(3-amino-2,6-dinitro-4-trifluoromethylphenyl)-1,1-diethylhydrazine. 6.A compound of claim 1 which is2-(3-amino-4-chloro-2,6-dinitrophenyl)-1,1-diethylhydrazine.
 7. Acompound of claim 1 which is2-(3-amino-4-trifluoromethyl-2,6-dinitrophenyl)-1,1,2-trimethylhydrazine.8. A compound of claim 1 which is2-(3-methylamino-4-trifluoromethyl-2,6-dinitrophenyl)-1,1-diethylhydrazine.9. A compound of claim 1 which is2-(3-dimethylamino-2,6-dinitro-4-trifluoromethylphenyl)-1,1-dimethylhydrazine.
 10. A compound of claim 1 which is2-(3-propylamino-2,6-dinitro-4-trifluoromethylphenyl)-1,1-dimethylhydrazine.